TWI707724B - Pd-catalyzed decomposition of formic acid - Google Patents

Pd-catalyzed decomposition of formic acid Download PDF

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TWI707724B
TWI707724B TW107127010A TW107127010A TWI707724B TW I707724 B TWI707724 B TW I707724B TW 107127010 A TW107127010 A TW 107127010A TW 107127010 A TW107127010 A TW 107127010A TW I707724 B TWI707724 B TW I707724B
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桑睿
劉劼
董開武
雷夫 傑克斯泰爾
馬席爾斯 貝勒
羅柏特 法蘭克
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Abstract

Process for Pd-catalyzed decomposition of formic acid

Description

Ｐｄ催化之甲酸分解方法Pd-catalyzed formic acid decomposition method

本發明係關於一種Pd催化之甲酸(HCOOH)分解方法。The present invention relates to a Pd-catalyzed formic acid (HCOOH) decomposition method.

甲酸在化學反應中係用作例如酸或溶劑，但也可能以反應副產物的形式產生。由於其腐蝕性質或發散強烈氣味的性質，可能會想要移除該甲酸。Formic acid is used as an acid or solvent in a chemical reaction, but it may also be produced as a by-product of the reaction. It may be desirable to remove the formic acid due to its corrosive or strong smelling properties.

本發明針對其目的必須提供一種方法，其中甲酸係在催化方法的幫助下有效率地分解。 該目的係藉由如申請專利範圍第1項之方法達成。 一種方法，其包含下列方法步驟： a)提供甲酸； b)添加包含Pd之化合物，其中該Pd能形成錯合物； c)添加通式(I)之化合物：

Figure 02_image001
其中R1 、R2 、R3 、R4 各自獨立選自：-H、-(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、-(C4 -C14 )-芳基、-O-(C4 -C14 )-芳基、環烷基、-(C1 -C12 )-雜烷基、-O-(C1 -C12 )-雜烷基、 -(C3 -C14 )-雜芳基、-O-(C3 -C14 )-雜芳基、-COO-烷基、 -COO-芳基、-C-O-烷基、-C-O-芳基、NH2 、鹵素且該等殘基也能形成較大稠合環； 其中所列舉之烷基基團、芳基基團、環烷基、雜烷基基團、雜芳基基團可經如下者取代： -(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、鹵素； 且該等基團R1 、R2 、R3 、R4 之至少一者不表示苯基； d)添加MeOH； e)加熱反應混合物以分解該甲酸。 在該方法之一變化型中，在方法步驟b)中之化合物係選自：Pd(acac)2 、PdCl2 、Pd(dba)3 *CH3 Cl(dba=二(苯亞甲基)丙酮)、Pd(OAc)2 、Pd(TFA)2 、Pd(CH3 CN)Cl2 。 在該方法之一變化型中，該方法步驟b)中之化合物是Pd(OAc)2 。 在該方法之一變化型中，該方法包含額外方法步驟f)： f)添加酸。 在該方法之一變化型中，在方法步驟f)中該酸係選自：H2 SO4 、CH3 SO3 H、CF3 SO3 H、PTSA。 在該方法之一變化型中，在方法步驟f)中該酸是PTSA。 在該方法之一變化型中，R1 、R2 、R3 、R4 各自獨立選自：-(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、-(C4 -C14 )-芳基、 -O-(C4 -C14 )-芳基、環烷基、-(C1 -C12 )-雜烷基、-O-(C1 -C12 )-雜烷基、-(C3 -C14 )-雜芳基、-O-(C3 -C14 )-雜芳基、 -COO-烷基、-COO-芳基、-C-O-烷基、-C-O-芳基、NH2 、鹵素且該等殘基也能形成較大稠合環； 其中所列舉之烷基基團、芳基基團、環烷基、雜烷基基團、雜芳基基團可經如下者取代： -(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、鹵素； 且該等基團R1 、R2 、R3 、R4 之至少一者不表示苯基。 在該方法之一變化型中，R1 、R2 、R3 、R4 各自獨立選自：-(C1 -C12 )-烷基、-(C4 -C14 )-芳基、環烷基、-(C1 -C12 )-雜烷基、-(C3 -C14 )-雜芳基、鹵素且該等殘基也能形成較大稠合環； 其中所列舉之烷基基團、芳基基團、環烷基、雜烷基基團、雜芳基基團可經如下者取代： -(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、鹵素； 且該等基團R1 、R2 、R3 、R4 之至少一者不表示苯基。 在該方法之一變化型中，R1 、R2 、R3 、R4 各自獨立選自：-(C1 -C12 )-烷基、環烷基、-(C3 -C14 )-雜芳基且該等殘基也能形成較大稠合環； 其中所列舉之烷基基團、環烷基、雜芳基基團可經如下者取代： -(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、鹵素； 且該等基團R1 、R2 、R3 、R4 之至少一者不表示苯基。 在該方法之一變化型中，R1 、R4 各自獨立選自：-(C1 -C12 )-烷基、環烷基且該等殘基也能形成較大稠合環； 其中所列舉之烷基基團、環烷基可經如下者取代： -(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、鹵素。 在該方法之一變化型中，R2 、R3 各自獨立表示：-(C3 -C14 )-雜芳基， 其中所列舉之雜芳基基團可經如下者取代： -(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、鹵素。 在該方法之一變化型中，通式(I)之化合物係選自結構(1)至(3)：
Figure 02_image003
Figure 02_image005
。 在該方法之一變化型中，通式(I)之化合物具有該結構(2)：
Figure 02_image007
。 在該方法之一變化型中，通式(I)之化合物具有該結構(3)：
Figure 02_image009
本發明藉由實例在下文中詳細闡明。The present invention must provide a method for its purpose in which formic acid is efficiently decomposed with the help of a catalytic method. This purpose is achieved by the method as in item 1 of the scope of patent application. A method comprising the following method steps: a) providing formic acid; b) adding a compound containing Pd, wherein the Pd can form a complex compound; c) adding a compound of general formula (I):
Figure 02_image001
Wherein R 1 , R 2 , R 3 , and R 4 are each independently selected from: -H, -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl, -(C 4 -C 14 )-aryl, -O-(C 4 -C 14 )-aryl, cycloalkyl, -(C 1 -C 12 )-heteroalkyl, -O-(C 1 -C 12 )- Heteroalkyl, -(C 3 -C 14 )-heteroaryl, -O-(C 3 -C 14 )-heteroaryl, -COO-alkyl, -COO-aryl, -CO-alkyl, -CO-aryl, NH 2 , halogen and these residues can also form larger condensed rings; the alkyl groups, aryl groups, cycloalkyl groups, heteroalkyl groups, and heteroaryl groups listed therein The group can be substituted by the following: -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl, halogen; and these groups R 1 , R 2 , R 3 , At least one of R 4 does not represent a phenyl group; d) adding MeOH; e) heating the reaction mixture to decompose the formic acid. In a variant of this method, the compound in step b) of the method is selected from: Pd(acac) 2 , PdCl 2 , Pd(dba) 3 *CH 3 Cl(dba=bis(benzylidene)acetone ), Pd(OAc) 2 , Pd(TFA) 2 , Pd(CH 3 CN)Cl 2 . In a variant of the method, the compound in step b) of the method is Pd(OAc) 2 . In a variant of the method, the method comprises an additional method step f): f) adding acid. In a variant of the method, in method step f) the acid is selected from: H 2 SO 4 , CH 3 SO 3 H, CF 3 SO 3 H, PTSA. In a variant of this method, the acid in method step f) is PTSA. In a variant of this method, R 1 , R 2 , R 3 , and R 4 are each independently selected from: -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl , -(C 4 -C 14 )-aryl, -O-(C 4 -C 14 )-aryl, cycloalkyl, -(C 1 -C 12 )-heteroalkyl, -O-(C 1 -C 12 )-heteroalkyl, -(C 3 -C 14 )-heteroaryl, -O-(C 3 -C 14 )-heteroaryl, -COO-alkyl, -COO-aryl,- CO-alkyl, -CO-aryl, NH 2 , halogen and these residues can also form larger condensed rings; the alkyl groups, aryl groups, cycloalkyl groups, heteroalkyl groups listed therein Groups and heteroaryl groups can be substituted by the following: -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl, halogen; and these groups R 1 , At least one of R 2 , R 3 , and R 4 does not represent a phenyl group. In a variant of this method, R 1 , R 2 , R 3 , and R 4 are each independently selected from: -(C 1 -C 12 )-alkyl, -(C 4 -C 14 )-aryl, ring Alkyl, -(C 1 -C 12 )-heteroalkyl, -(C 3 -C 14 )-heteroaryl, halogen, and these residues can also form larger fused rings; the alkyl groups listed therein Groups, aryl groups, cycloalkyl groups, heteroalkyl groups, and heteroaryl groups may be substituted with the following: -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-Alkyl, halogen; and at least one of these groups R 1 , R 2 , R 3 , and R 4 does not represent a phenyl group. In a variation of this method, R 1 , R 2 , R 3 , and R 4 are each independently selected from: -(C 1 -C 12 )-alkyl, cycloalkyl, -(C 3 -C 14 )- Heteroaryl groups and these residues can also form larger fused rings; the alkyl groups, cycloalkyl groups, and heteroaryl groups listed therein can be substituted by the following: -(C 1 -C 12 )- Alkyl group, -O-(C 1 -C 12 )-alkyl group, halogen; and at least one of these groups R 1 , R 2 , R 3 , and R 4 does not represent a phenyl group. In a variant of this method, R 1 and R 4 are each independently selected from: -(C 1 -C 12 )-alkyl, cycloalkyl, and these residues can also form larger fused rings; The enumerated alkyl groups and cycloalkyl groups can be substituted by the following: -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl, halogen. In a variant of this method, R 2 and R 3 each independently represent: -(C 3 -C 14 )-heteroaryl, wherein the listed heteroaryl groups can be substituted by the following: -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl, halogen. In a variant of this method, the compound of general formula (I) is selected from structures (1) to (3):
Figure 02_image003
Figure 02_image005
. In a variant of this method, the compound of general formula (I) has the structure (2):
Figure 02_image007
. In a variant of this method, the compound of general formula (I) has the structure (3):
Figure 02_image009
The present invention is illustrated in detail below with examples.

Pd催化之甲酸分解的調查

Figure 02_image011
在氬氣氛下，將[Pd(OAc)2 ](4.48 mg, 0.02 mmol, 0.05 mol%)、配位基L(0.08 mmol, 0.2 mol%)、PTSA·H2 O(76 mg, 0.4 mmol, 1.0 mol%)導入壓熱器中(在個別實驗中照著下表避開個別成分之添加。)隨後，利用注射器注射MeOH(6.5 ml)和HCOOH(40 mmol, 1.50 ml)。然後該壓熱器以氮(5巴)沖洗三次。將反應混合物加熱至100℃且維持在此溫度下18小時。在此時間後，將該壓熱器冷卻至室溫。 壓力係藉由電子式壓熱器壓力紀錄感測器測量。 CO、H2 和CO2 之選擇率係藉由氣體GC分析測定。 結果摘錄於下表中：
Figure 02_image013
如上述實驗顯示的，該目的係藉由根據本發明之方法達成。Investigation of formic acid decomposition catalyzed by Pd
Figure 02_image011
In an argon atmosphere, [Pd(OAc) 2 ] (4.48 mg, 0.02 mmol, 0.05 mol%), ligand L (0.08 mmol, 0.2 mol%), PTSA·H 2 O (76 mg, 0.4 mmol, 1.0 mol%) was introduced into the autoclave (in individual experiments, the addition of individual ingredients was avoided according to the following table.) Then, MeOH (6.5 ml) and HCOOH (40 mmol, 1.50 ml) were injected with a syringe. The autoclave was then flushed three times with nitrogen (5 bar). The reaction mixture was heated to 100°C and maintained at this temperature for 18 hours. After this time, the autoclave was cooled to room temperature. The pressure is measured by an electronic autoclave pressure recording sensor. The selectivity of CO, H 2 and CO 2 is determined by gas GC analysis. The results are excerpted in the table below:
Figure 02_image013
As the above experiment shows, this objective is achieved by the method according to the present invention.

Claims (8)

一種Pd催化之甲酸分解方法，其包含下列方法步驟：a)提供甲酸；b)添加包含Pd之化合物，其中該Pd能形成錯合物；c)添加選自以下結構(2)或(3)之化合物：
Figure 107127010-A0305-02-0009-1
Figure 107127010-A0305-02-0009-2
 d)添加MeOH；e)加熱反應混合物以分解該甲酸。 A Pd-catalyzed formic acid decomposition method, which comprises the following method steps: a) providing formic acid; b) adding a compound containing Pd, wherein the Pd can form a complex; c) adding a structure selected from the following structures (2) or (3) The compound:
Figure 107127010-A0305-02-0009-1
Figure 107127010-A0305-02-0009-2
 d) Add MeOH; e) Heat the reaction mixture to decompose the formic acid. 如申請專利範圍第1項之方法，其中在方法步驟b)中之化合物係選自：Pd(acac)2、PdCl2、Pd(dba)3*CH3Cl(dba=二(苯亞甲基)丙酮)、Pd(OAc)2、Pd(TFA)2、Pd(CH3CN)Cl2。 Such as the method of item 1 in the scope of the patent application, wherein the compound in step b) of the method is selected from: Pd(acac) 2 , PdCl 2 , Pd(dba) 3 *CH 3 Cl(dba=bis(phenylmethylene ) Acetone), Pd(OAc) 2 , Pd(TFA) 2 , Pd(CH 3 CN)Cl 2 . 如申請專利範圍第1或2項之方法， 其中該方法步驟b)中之化合物是Pd(OAc)2。 Such as the method of item 1 or 2 in the scope of patent application, wherein the compound in step b) of the method is Pd(OAc) 2 . 如申請專利範圍第1項之方法，其中該方法包含額外方法步驟f)：f)添加酸。 Such as the method of item 1 in the scope of patent application, wherein the method includes additional method steps f): f) adding acid. 如申請專利範圍第4項之方法，其中在方法步驟f)中該酸係選自：H2SO4、CH3SO3H、CF3SO3H、PTSA。 Such as the method of item 4 in the scope of patent application, wherein in step f) of the method, the acid is selected from: H 2 SO 4 , CH 3 SO 3 H, CF 3 SO 3 H, and PTSA. 如申請專利範圍第4和5項中任一項之方法，其中在方法步驟f)中該酸是PTSA。 Such as the method of any one of items 4 and 5 in the scope of patent application, wherein the acid in step f) of the method is PTSA. 如申請專利範圍第1項之方法，其中該化合物具有該結構(2)：
Figure 107127010-A0305-02-0010-3
 For example, the method of item 1 in the scope of patent application, wherein the compound has the structure (2):
Figure 107127010-A0305-02-0010-3
 如申請專利範圍第1項之方法，其中該化合物具有該結構(3)：
Figure 107127010-A0305-02-0011-4
 Such as the method of item 1 in the scope of patent application, wherein the compound has the structure (3):
Figure 107127010-A0305-02-0011-4
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